Ab initio simulation of laser-induced electronic and vibrational coherence

TL;DR

This paper introduces a quantum-semiclassical RT-TDDFT+Ehrenfest method to simulate laser-induced electronic and vibrational coherences, addressing thermal effects and zero-point energies, and enabling first-principles studies of nonlinear spectroscopy.

Contribution

The study develops an ensemble-averaged RT-TDDFT+Ehrenfest approach that improves accuracy in simulating laser-induced coherences in condensed matter, especially for large systems.

Findings

Ensemble averaging remedies damping of electronic coherence.

Method captures ultrafast non-adiabatic couplings.

Computational costs remain moderate for large systems.

Abstract

The atomistic resolution recently achieved by ultrafast spectroscopies demands corresponding theoretical advances. Real-time time-dependent density-functional theory (RT-TDDFT) with Ehrenfest dynamics offers an optimal trade-off between accuracy and computational costs to study electronic and vibrational dynamics of laser-excited materials in the sub-picosecond regime. However, this approach is unable to account for thermal effects or zero-point energies which are crucial in the physics involved. Herein, we adopt a quantum-semiclassical method based on RT-TDDFT+Ehrenfest to simulate laser-induced electronic and vibrational coherences in condensed matter. With the example of carbon-conjugated molecules, we show that ensemble-averaging with initial configurations from a nuclear quantum distribution remedies many shortcomings of single-trajectory RT-TDDFT+Ehrenfest, damping electronic coherence and introducing ultrafast non-adiabatic coupling between excited states. As the number of sampled configurations decreases with size and rigidity of the compounds, computational costs remain moderate for large systems for which mean-field approaches shine. The explicit inclusion of a time-dependent pulse in the simulations makes this method a prime advance for first-principles studies of coherent nonlinear spectroscopy as an independent counterpart to experimental results.